Wechselwirkungen in Kristallen. 136. Protonierte Di(pyrid-2-yl)amin-Salze mit verschiedenen Anionen: Monomeres Tetraphenylborat sowie Bis(trifluormethylsulfonat), dimeres Squarat und polymeres Chlorid-Dihydrat

Abstract

Interactions in Crystals. 136. Protonated Dipyridylamine Salts with Different Anions: Monomeric Tetraphenylborate as well as Bis(trifluormethylsulfonate), Dimeric Squarate and Polymeric Chloride Dihydrate Di(pyrid‐2‐yl)amine is monoprotonated by acetic, squaric as well as hydrochloric acid and diprotonated by trifluoromethylsulfonic acid. To explore the anion and hydrogen‐bridge dependency of its salts, crystals of the monomeric tetraphenylborate, the dimeric squarate as well as the bis(trifluoromethylsulfonate) and the polymeric chloride hydrate have been grown and their structures determined: Separated by bulky tetraphenylborate anions, pyrid‐2‐yl(2′‐pyridinium) amine cation contains an intramolecular hydrogen bridge N⊕H…︁N and is slightly folded. The squarate salt dimer exhibits additional bridges, NH…︁O⊖ and OH…︁O. The severely twisted di(2‐pyridinium)amine dication is connected to its trifluormethylsulfonate counter anions by altogether three H‐bridges, two N⊕H…︁O and one NH…︁O. The chloride dihydrate crystallizes in layers of 16‐membered rings, formed from three Cl anions and five water molecules. The diversity of the hydrogen‐bridge dominated salt structures is discussed based on comparison with selected literature examples and on PM3 calculations.

2-(Pyridin-2-ylamino)pyridinium thiocyanate acetonitrile monosolvate

“…The aromatic systems are nearly coplanar, the least-squares planes defined by their respective atoms form very small dihedral angle of 1.99 (4) °. These observations are in good agreement with the geometrical parameters reported for similar compounds such as the chloride (Bock et al, 1998), the bromide (Junk et al, 2006) or the nitrate (Du & Zhao, 2004). In contrast to unprotonated dipyridine-2-ylamine, the title compound features the aromatic-ring-containing entity in a conformation with the pyridine nitrogen atoms facing each other.…”

“…For the crystal structure of dipyridin-2-ylamine, see for example : Johnson & Jacobson (1973); Pyrka & Pinkerton (1992); Schö del et al (1996). For the crystal structures of comparable chloride, bromide and nitrate salts, see: Bock et al (1998);Junk et al (2006); Du & Zhao (2004). For the use of chelating ligands in coordination chemistry, see: Gade (1998).…”

Applying Ni(II) Amine Complexes and Sodium Thiostannate as Educts for the Generation of Thiostannates at Room Temperature

“…The layers are connected via the Ni 2+ centered complexes, that are located in the pores of the water cluster forming a 3D network. Involvement of anions in H bonding to water clusters is not rare and is, e.g., observed with Cl – anions forming L8(6) layers − or [S 4 O 6 ] 2– anions leading to a L20(6) motif …”

Hydrogen-bond landscapes, geometry and energetics of squaric acid and its mono- and dianions: a Cambridge Structural Database, IsoStar and computational study

“…Almost half (47%) of the HSQ À structures contain a dimer synthon (Desiraju, 1995). These dimers are almost always linked into chains or other extended structures via N-HÁ Á ÁO hydrogen bonds from counterions, as in BOLFUD (Bock et al, 1998;Fig. 3a) where the counterion is pyrid-2-yl(2 0 -pyridinium)amine.…”

“…The most obvious feature of the packing of the aromatic SQ 2À dianions is the occurrence of stacked rings in 18 of the 46 structures. The stacking may be characterized by d 1 , the perpendicular distance between the ring planes, and d 2 , the distance between ring centroids, from which the offset from a research papers Dimer and catena synthons in the crystal structures of HSQ À compounds: (a) the HSQ À dimer synthon in BOLFUD (Bock et al, 1998) where the counterion is pyrid-2-yl(2 0 -pyridinium)amine; (b) the HSQ À catena synthon in TIWWUR (Karle et al, 1996) where the counterion is imidazolium; (c) the HSQ À catena synthon in LUVTOL (Mattes et al, 2003) where the counterion is pyrimidinium. perfect overlay of ring centroids, d 3 , can readily be calculated.…”